Molecular origins of commercial laser dye functionality in azacoumarins and 2-quinolones: LD 425, LD 489 and LD 473

The molecular structures of three compounds, LD 425 (C₁₃H₁₄N₂O₃) (1), LD 489 (C₁₅H₁₅F₃N₂O₂) (2) and LD 473 (C₁₇H₁₉F₃N₂O) (3), are determined by single-crystal X-ray diffraction (XRD) at 180 K. Azacoumarins (1) and (2) possess para-quinoidal bond-length patterns in their benzene rings due to intramolecular charge transfer (ICT) from these rings to the adjoining rings. In contrast, substitution of O with N within the coumarin heterocycle, to form a 2-quinolone, results in the suppression of this ICT effect. Instead, charge transfer within the heterocycle is shown to become more pronounced. Resonance theory is employed to discuss these bond pattern differences and characteristic spectral blue shifts in relation to their coumarin analogues. The application of this theory offers an intuitive understanding of the structure-property relationships in azacoumarins and 2-quinolones which is further supported by quantum chemical calculations. Such an understanding is important for recognizing ICT mechanisms in these compounds which can then be used to facilitate the molecular design of new laser dyes with the desired spectral shifts.

Computing details

Data collection: Rigaku CrystalClear-SM Expert 2.0 r4 for ld425; COLLECT (Nonius BV, 1998) for ld489, ld473. Cell refinement: Rigaku CrystalClear-SM Expert 2.0 r4 for ld425; ? for ld489. Data reduction: Rigaku CrystalClear-SM Expert 2.0 r4 for ld425; ? for ld489. For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) for ld489, ld473. Software used to prepare material for publication: publCIF (Westrip, 2010) for ld489, ld473.

Figures

(ld425)

Crystal data

C13H14N2O3	F(000) = 1040
Mr = 246.26	Dx = 1.397 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6908 reflections
a = 7.061 (5) Å	θ = 1.7–33.1°
b = 24.489 (15) Å	µ = 0.10 mm^−1
c = 13.930 (9) Å	T = 180 K
β = 103.481 (8)°	Platelet, colorless
V = 2342 (3) Å^3	0.56 × 0.28 × 0.11 mm
Z = 8

Data collection

Rigaku CrystalClear-SM Expert 2.0 r4 diffractometer	5763 independent reflections
Radiation source: fine-focus sealed tube	4634 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.077
Detector resolution: 28.5714 pixels mm^-1	θmax = 28.3°, θmin = 2.9°
profile data from ω–scans	h = −9→9
Absorption correction: multi-scan Scaled and merged with SORTAV R.H. Blessing, (1987) Cryst. Rev. 1, 3-58 R.H. Blessing, (1989) J. Appl. Cryst. 22, 396-397	k = −32→32
Tmin = 0.973, Tmax = 1.028	l = −18→18
14043 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.158	All H-atom parameters refined
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0464P)^2 + 0.1911P] where P = (Fo^2 + 2Fc^2)/3
5763 reflections	(Δ/σ)max = 0.001
437 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.49 e Å^−3

Special details

Experimental. Rigaku CrystalClear-SM Expert 2.0 r4

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.9461 (3)	0.32749 (8)	0.51150 (14)	0.0365 (4)
C2	1.0239 (3)	0.31857 (6)	0.79281 (13)	0.0289 (4)
C3	0.9999 (3)	0.33907 (6)	0.69354 (13)	0.0285 (3)
C4	0.9731 (3)	0.30570 (6)	0.61449 (12)	0.0269 (3)
C5	0.9466 (3)	0.20756 (7)	0.55654 (13)	0.0289 (3)
C6	0.9456 (3)	0.15300 (7)	0.58036 (13)	0.0297 (4)
C7	0.9653 (3)	0.13818 (6)	0.68034 (13)	0.0274 (3)
C8	0.9912 (2)	0.22765 (6)	0.72641 (12)	0.0253 (3)
C9	0.9689 (3)	0.24746 (6)	0.63058 (12)	0.0254 (3)
C10	0.8563 (3)	−0.00960 (7)	0.67249 (16)	0.0375 (4)
C11	0.9627 (3)	0.03917 (7)	0.64244 (15)	0.0342 (4)
C12	1.0232 (3)	0.07002 (7)	0.81380 (14)	0.0368 (4)
C13	0.9132 (4)	0.02028 (7)	0.83592 (16)	0.0392 (4)
N1	0.9903 (2)	0.17579 (5)	0.75302 (10)	0.0282 (3)
N2	0.9565 (2)	0.08469 (5)	0.70933 (11)	0.0312 (3)
O1	1.0178 (2)	0.26266 (4)	0.80581 (9)	0.0303 (3)
O2	1.0474 (2)	0.34628 (5)	0.86719 (9)	0.0387 (3)
O3	0.9335 (2)	−0.02438 (5)	0.77298 (11)	0.0392 (3)
H3	1.007 (3)	0.3794 (9)	0.6895 (15)	0.033 (5)*
H5	0.932 (3)	0.2178 (9)	0.4859 (16)	0.040 (6)*
H6	0.933 (4)	0.1269 (10)	0.5321 (17)	0.044 (6)*
H10A	0.718 (4)	−0.0011 (9)	0.6641 (16)	0.040 (6)*
H11A	0.894 (4)	0.0492 (9)	0.5699 (17)	0.041 (6)*
H12A	0.994 (4)	0.1002 (10)	0.8522 (18)	0.049 (7)*
H13A	0.767 (4)	0.0294 (9)	0.8267 (17)	0.047 (7)*
H10B	0.873 (3)	−0.0424 (8)	0.6329 (15)	0.032 (5)*
H11B	1.096 (4)	0.0303 (9)	0.6439 (16)	0.039 (6)*
H12B	1.163 (3)	0.0635 (9)	0.8302 (16)	0.034 (6)*
H13B	0.975 (3)	0.0070 (9)	0.9046 (17)	0.042 (6)*
H1A	0.813 (4)	0.3148 (10)	0.4693 (17)	0.052 (7)*
H1B	0.952 (4)	0.3694 (9)	0.5139 (16)	0.043 (6)*
H1C	1.044 (4)	0.3129 (10)	0.4814 (17)	0.050 (7)*
C1'	0.5723 (3)	0.60840 (7)	0.95517 (14)	0.0351 (4)
C2'	0.5056 (3)	0.63447 (7)	0.67842 (13)	0.0311 (4)
C3'	0.5351 (3)	0.60840 (6)	0.77339 (13)	0.0296 (4)
C4'	0.5482 (3)	0.63685 (6)	0.85765 (13)	0.0278 (3)
C5'	0.5510 (3)	0.73147 (7)	0.93349 (13)	0.0291 (4)
C6'	0.5393 (3)	0.78692 (7)	0.91930 (13)	0.0300 (4)
C7'	0.5129 (3)	0.80747 (6)	0.82181 (13)	0.0274 (3)
C8'	0.5105 (3)	0.72095 (6)	0.76077 (12)	0.0267 (3)
C9'	0.5359 (2)	0.69574 (6)	0.85298 (12)	0.0262 (3)
C10'	0.4305 (3)	0.95433 (7)	0.84990 (16)	0.0381 (4)
C11'	0.5584 (3)	0.90424 (7)	0.87593 (15)	0.0346 (4)
C12'	0.4811 (3)	0.88138 (7)	0.70015 (14)	0.0340 (4)
C13'	0.3556 (3)	0.93232 (7)	0.68180 (16)	0.0371 (4)
N1'	0.4991 (2)	0.77406 (6)	0.74347 (10)	0.0284 (3)
N2'	0.4932 (3)	0.86204 (5)	0.80112 (11)	0.0324 (3)
O1'	0.4949 (2)	0.69094 (5)	0.67596 (9)	0.0313 (3)
O2'	0.4875 (2)	0.61180 (5)	0.59927 (10)	0.0411 (3)
O3'	0.4279 (2)	0.97386 (5)	0.75282 (11)	0.0387 (3)
H3'	0.538 (3)	0.5695 (10)	0.7721 (16)	0.039 (6)*
H5'	0.566 (3)	0.7175 (9)	1.0013 (15)	0.036 (6)*
H6'	0.547 (3)	0.8105 (9)	0.9725 (15)	0.037 (6)*
H10C	0.289 (4)	0.9457 (9)	0.8536 (17)	0.044 (6)*
H11C	0.554 (4)	0.8922 (9)	0.9401 (17)	0.040 (6)*
H12C	0.419 (4)	0.8540 (9)	0.6579 (16)	0.043 (6)*
H13C	0.215 (3)	0.9233 (9)	0.6834 (16)	0.037 (6)*
H10D	0.482 (3)	0.9822 (9)	0.8955 (16)	0.039 (6)*
H11D	0.696 (4)	0.9148 (10)	0.8762 (17)	0.046 (6)*
H12D	0.616 (3)	0.8896 (9)	0.6928 (15)	0.032 (5)*
H13D	0.366 (4)	0.9486 (9)	0.6128 (17)	0.044 (6)*
H1D	0.459 (4)	0.6172 (9)	0.9843 (17)	0.043 (6)*
H1E	0.588 (4)	0.5682 (10)	0.9486 (17)	0.044 (6)*
H1F	0.684 (4)	0.6220 (9)	1.0033 (17)	0.041 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0478 (12)	0.0315 (8)	0.0297 (9)	0.0035 (8)	0.0077 (8)	0.0065 (7)
C2	0.0347 (9)	0.0217 (7)	0.0310 (8)	−0.0027 (6)	0.0094 (7)	−0.0014 (6)
C3	0.0322 (9)	0.0226 (7)	0.0319 (8)	0.0007 (6)	0.0098 (7)	0.0016 (6)
C4	0.0263 (8)	0.0249 (7)	0.0297 (8)	0.0020 (6)	0.0071 (7)	0.0039 (6)
C5	0.0319 (9)	0.0269 (7)	0.0289 (8)	−0.0004 (6)	0.0087 (7)	−0.0021 (6)
C6	0.0340 (9)	0.0254 (7)	0.0312 (8)	−0.0011 (7)	0.0102 (7)	−0.0049 (6)
C7	0.0285 (8)	0.0221 (7)	0.0331 (8)	0.0003 (6)	0.0104 (7)	−0.0011 (6)
C8	0.0267 (8)	0.0232 (7)	0.0273 (8)	0.0003 (6)	0.0086 (6)	−0.0009 (6)
C9	0.0264 (8)	0.0232 (7)	0.0266 (8)	0.0009 (6)	0.0060 (6)	0.0000 (6)
C10	0.0377 (10)	0.0242 (7)	0.0496 (11)	−0.0027 (7)	0.0081 (9)	−0.0028 (7)
C11	0.0408 (10)	0.0227 (7)	0.0417 (10)	−0.0007 (7)	0.0146 (8)	−0.0053 (7)
C12	0.0506 (12)	0.0240 (7)	0.0360 (9)	−0.0043 (8)	0.0105 (9)	0.0016 (7)
C13	0.0494 (12)	0.0257 (8)	0.0457 (11)	−0.0010 (8)	0.0175 (10)	0.0033 (7)
N1	0.0339 (8)	0.0213 (6)	0.0304 (7)	−0.0009 (5)	0.0097 (6)	0.0005 (5)
N2	0.0403 (9)	0.0204 (6)	0.0341 (7)	−0.0012 (6)	0.0110 (7)	−0.0011 (5)
O1	0.0444 (8)	0.0208 (5)	0.0265 (6)	−0.0017 (5)	0.0100 (5)	0.0002 (4)
O2	0.0597 (10)	0.0257 (5)	0.0324 (7)	−0.0051 (6)	0.0142 (7)	−0.0041 (5)
O3	0.0437 (8)	0.0213 (5)	0.0524 (8)	−0.0007 (5)	0.0110 (7)	0.0027 (5)
C1'	0.0441 (11)	0.0280 (8)	0.0324 (9)	−0.0003 (8)	0.0072 (8)	0.0054 (7)
C2'	0.0338 (9)	0.0241 (7)	0.0346 (9)	0.0025 (6)	0.0065 (7)	−0.0014 (6)
C3'	0.0329 (9)	0.0200 (7)	0.0347 (9)	−0.0001 (6)	0.0056 (7)	0.0011 (6)
C4'	0.0247 (8)	0.0242 (7)	0.0335 (8)	−0.0015 (6)	0.0048 (7)	0.0017 (6)
C5'	0.0317 (9)	0.0262 (7)	0.0300 (8)	−0.0018 (6)	0.0084 (7)	0.0016 (6)
C6'	0.0344 (9)	0.0257 (7)	0.0314 (8)	−0.0015 (7)	0.0109 (7)	−0.0034 (6)
C7'	0.0267 (8)	0.0228 (7)	0.0337 (8)	0.0001 (6)	0.0093 (7)	0.0005 (6)
C8'	0.0277 (8)	0.0237 (7)	0.0290 (8)	−0.0005 (6)	0.0071 (7)	−0.0021 (6)
C9'	0.0251 (8)	0.0232 (7)	0.0298 (8)	−0.0013 (6)	0.0059 (7)	0.0018 (6)
C10'	0.0445 (11)	0.0236 (7)	0.0503 (11)	0.0004 (8)	0.0197 (9)	−0.0037 (7)
C11'	0.0441 (11)	0.0235 (7)	0.0385 (9)	−0.0015 (7)	0.0139 (8)	−0.0023 (7)
C12'	0.0437 (11)	0.0238 (7)	0.0369 (9)	0.0032 (7)	0.0144 (8)	0.0027 (7)
C13'	0.0399 (11)	0.0246 (7)	0.0466 (11)	0.0022 (7)	0.0099 (9)	0.0022 (7)
N1'	0.0327 (8)	0.0230 (6)	0.0295 (7)	0.0018 (5)	0.0074 (6)	0.0015 (5)
N2'	0.0452 (9)	0.0204 (6)	0.0336 (7)	0.0009 (6)	0.0132 (7)	0.0005 (5)
O1'	0.0413 (7)	0.0227 (5)	0.0293 (6)	0.0024 (5)	0.0073 (5)	0.0004 (4)
O2'	0.0603 (10)	0.0289 (6)	0.0327 (7)	0.0056 (6)	0.0079 (7)	−0.0038 (5)
O3'	0.0457 (8)	0.0209 (5)	0.0507 (8)	−0.0011 (5)	0.0137 (7)	0.0008 (5)

Geometric parameters (Å, º)

C6—C7	1.414 (3)	C10—C11	1.521 (3)
C7—N1	1.350 (2)	C10—H10A	0.98 (2)
C8—N1	1.324 (2)	C10—H10B	1.00 (2)
C8—C9	1.394 (2)	C11—N2	1.460 (2)
C5—C9	1.403 (2)	C11—H11A	1.04 (2)
C5—C6	1.377 (2)	C11—H11B	0.96 (2)
C8—O1	1.377 (2)	C12—N2	1.466 (2)
C2—O1	1.383 (2)	C12—C13	1.514 (3)
C2—C3	1.444 (2)	C12—H12A	0.96 (3)
C3—C4	1.349 (2)	C12—H12B	0.98 (2)
C4—C9	1.445 (2)	C13—O3	1.430 (2)
C2—O2	1.217 (2)	C13—H13A	1.03 (3)
C6'—C7'	1.419 (2)	C13—H13B	1.01 (2)
C7'—N1'	1.349 (2)	C1'—C4'	1.501 (2)
C8'—N1'	1.322 (2)	C1'—H1D	1.00 (3)
C8'—C9'	1.398 (2)	C1'—H1E	1.00 (2)
C5'—C9'	1.407 (2)	C1'—H1F	0.97 (2)
C5'—C6'	1.372 (2)	C3'—H3'	0.95 (2)
C8'—O1'	1.374 (2)	C5'—H5'	0.99 (2)
C2'—O1'	1.385 (2)	C6'—H6'	0.93 (2)
C2'—C3'	1.440 (2)	C10'—O3'	1.431 (3)
C3'—C4'	1.349 (2)	C10'—C11'	1.516 (3)
C4'—C9'	1.445 (2)	C10'—H10C	1.04 (3)
C2'—O2'	1.214 (2)	C10'—H10D	0.95 (2)
C7—N2	1.376 (2)	C11'—N2'	1.464 (2)
C7'—N2'	1.367 (2)	C11'—H11C	0.95 (2)
C1—C4	1.501 (2)	C11'—H11D	1.00 (3)
C1—H1A	1.03 (3)	C12'—N2'	1.468 (2)
C1—H1B	1.03 (2)	C12'—C13'	1.517 (3)
C1—H1C	0.96 (3)	C12'—H12C	0.93 (2)
C3—H3	0.99 (2)	C12'—H12D	1.00 (2)
C5—H5	1.00 (2)	C13'—O3'	1.428 (2)
C6—H6	0.92 (2)	C13'—H13C	1.02 (2)
C10—O3	1.426 (3)	C13'—H13D	1.06 (2)
C4—C1—H1A	109.4 (13)	C4'—C1'—H1D	109.5 (13)
C4—C1—H1B	109.2 (12)	C4'—C1'—H1E	111.5 (13)
H1A—C1—H1B	109.9 (19)	H1D—C1'—H1E	111.6 (19)
C4—C1—H1C	110.0 (15)	C4'—C1'—H1F	111.8 (14)
H1A—C1—H1C	107.0 (19)	H1D—C1'—H1F	104.0 (19)
H1B—C1—H1C	111 (2)	H1E—C1'—H1F	108.2 (19)
O2—C2—O1	116.28 (15)	O2'—C2'—O1'	116.13 (16)
O2—C2—C3	125.72 (16)	O2'—C2'—C3'	126.42 (16)
O1—C2—C3	118.00 (14)	O1'—C2'—C3'	117.45 (15)
C4—C3—C2	122.28 (15)	C4'—C3'—C2'	122.42 (15)
C4—C3—H3	123.8 (12)	C4'—C3'—H3'	122.4 (13)
C2—C3—H3	113.9 (12)	C2'—C3'—H3'	115.1 (13)
C3—C4—C9	118.40 (15)	C3'—C4'—C9'	119.01 (15)
C3—C4—C1	121.83 (16)	C3'—C4'—C1'	121.19 (15)
C9—C4—C1	119.77 (15)	C9'—C4'—C1'	119.80 (15)
C6—C5—C9	120.31 (16)	C6'—C5'—C9'	120.66 (16)
C6—C5—H5	118.5 (13)	C6'—C5'—H5'	118.0 (12)
C9—C5—H5	121.2 (13)	C9'—C5'—H5'	121.3 (12)
C5—C6—C7	118.78 (15)	C5'—C6'—C7'	118.61 (16)
C5—C6—H6	120.3 (15)	C5'—C6'—H6'	120.6 (13)
C7—C6—H6	120.9 (15)	C7'—C6'—H6'	120.7 (13)
N1—C7—N2	115.86 (15)	N1'—C7'—N2'	115.96 (15)
N1—C7—C6	121.96 (15)	N1'—C7'—C6'	121.83 (15)
N2—C7—C6	122.17 (15)	N2'—C7'—C6'	122.17 (15)
N1—C8—O1	112.40 (14)	N1'—C8'—O1'	112.35 (15)
N1—C8—C9	126.53 (15)	N1'—C8'—C9'	126.23 (15)
O1—C8—C9	121.07 (14)	O1'—C8'—C9'	121.42 (15)
C8—C9—C5	115.46 (15)	C8'—C9'—C5'	115.30 (15)
C8—C9—C4	119.34 (15)	C8'—C9'—C4'	118.37 (15)
C5—C9—C4	125.20 (15)	C5'—C9'—C4'	126.31 (15)
O3—C10—C11	111.69 (16)	O3'—C10'—C11'	111.85 (16)
O3—C10—H10A	108.2 (13)	O3'—C10'—H10C	108.4 (13)
C11—C10—H10A	110.2 (13)	C11'—C10'—H10C	110.6 (13)
O3—C10—H10B	105.7 (12)	O3'—C10'—H10D	108.2 (14)
C11—C10—H10B	110.4 (12)	C11'—C10'—H10D	108.1 (14)
H10A—C10—H10B	110.5 (18)	H10C—C10'—H10D	109.7 (19)
N2—C11—C10	109.48 (16)	N2'—C11'—C10'	109.27 (17)
N2—C11—H11A	111.1 (13)	N2'—C11'—H11C	112.2 (14)
C10—C11—H11A	107.6 (13)	C10'—C11'—H11C	109.1 (14)
N2—C11—H11B	109.5 (13)	N2'—C11'—H11D	109.1 (14)
C10—C11—H11B	111.1 (14)	C10'—C11'—H11D	108.4 (14)
H11A—C11—H11B	107.9 (18)	H11C—C11'—H11D	108.7 (19)
N2—C12—C13	109.75 (17)	N2'—C12'—C13'	109.14 (16)
N2—C12—H12A	107.7 (15)	N2'—C12'—H12C	106.7 (14)
C13—C12—H12A	108.6 (15)	C13'—C12'—H12C	108.5 (15)
N2—C12—H12B	110.3 (13)	N2'—C12'—H12D	108.6 (12)
C13—C12—H12B	111.1 (13)	C13'—C12'—H12D	110.5 (12)
H12A—C12—H12B	109 (2)	H12C—C12'—H12D	113.3 (19)
O3—C13—C12	111.18 (17)	O3'—C13'—C12'	111.63 (17)
O3—C13—H13A	109.1 (13)	O3'—C13'—H13C	109.3 (12)
C12—C13—H13A	110.2 (13)	C12'—C13'—H13C	110.6 (12)
O3—C13—H13B	104.6 (13)	O3'—C13'—H13D	105.7 (12)
C12—C13—H13B	108.8 (13)	C12'—C13'—H13D	107.5 (13)
H13A—C13—H13B	112.8 (19)	H13C—C13'—H13D	112.1 (18)
C8—N1—C7	116.94 (15)	C8'—N1'—C7'	117.35 (15)
C7—N2—C11	121.95 (16)	C7'—N2'—C11'	122.71 (16)
C7—N2—C12	119.91 (14)	C7'—N2'—C12'	119.85 (15)
C11—N2—C12	113.31 (15)	C11'—N2'—C12'	113.14 (14)
C8—O1—C2	120.91 (13)	C8'—O1'—C2'	121.32 (14)
C10—O3—C13	109.75 (15)	C13'—O3'—C10'	109.91 (14)
C6—C7—N2—C11	11.6 (3)	C11—C10—O3—C13	60.5 (2)
N1—C7—N2—C12	−15.8 (3)	C12—C13—O3—C10	−60.7 (2)
C6'—C7'—N2'—C11'	20.3 (3)	O2'—C2'—C3'—C4'	−178.1 (2)
N1'—C7'—N2'—C12'	−6.8 (3)	O1'—C2'—C3'—C4'	1.4 (3)
O2—C2—C3—C4	−179.52 (19)	C2'—C3'—C4'—C9'	−1.2 (3)
O1—C2—C3—C4	−0.3 (3)	C2'—C3'—C4'—C1'	177.93 (18)
C2—C3—C4—C9	−0.1 (3)	C9'—C5'—C6'—C7'	−0.4 (3)
C2—C3—C4—C1	179.33 (18)	C5'—C6'—C7'—N1'	0.0 (3)
C9—C5—C6—C7	0.7 (3)	C5'—C6'—C7'—N2'	177.74 (18)
C5—C6—C7—N1	−1.8 (3)	N1'—C8'—C9'—C5'	−0.3 (3)
C5—C6—C7—N2	176.89 (18)	O1'—C8'—C9'—C5'	179.55 (16)
N1—C8—C9—C5	−1.1 (3)	N1'—C8'—C9'—C4'	−179.00 (17)
O1—C8—C9—C5	178.85 (15)	O1'—C8'—C9'—C4'	0.9 (3)
N1—C8—C9—C4	179.81 (18)	C6'—C5'—C9'—C8'	0.5 (3)
O1—C8—C9—C4	−0.2 (3)	C6'—C5'—C9'—C4'	179.12 (18)
C6—C5—C9—C8	0.7 (3)	C3'—C4'—C9'—C8'	0.0 (3)
C6—C5—C9—C4	179.70 (18)	C1'—C4'—C9'—C8'	−179.06 (16)
C3—C4—C9—C8	0.4 (3)	C3'—C4'—C9'—C5'	−178.50 (17)
C1—C4—C9—C8	−179.06 (17)	C1'—C4'—C9'—C5'	2.4 (3)
C3—C4—C9—C5	−178.56 (17)	O3'—C10'—C11'—N2'	−55.8 (2)
C1—C4—C9—C5	1.9 (3)	N2'—C12'—C13'—O3'	56.4 (2)
O3—C10—C11—N2	−55.6 (2)	O1'—C8'—N1'—C7'	−179.94 (15)
N2—C12—C13—O3	56.2 (2)	C9'—C8'—N1'—C7'	−0.1 (3)
O1—C8—N1—C7	−179.92 (15)	N2'—C7'—N1'—C8'	−177.62 (17)
C9—C8—N1—C7	0.0 (3)	C6'—C7'—N1'—C8'	0.2 (3)
N2—C7—N1—C8	−177.33 (17)	N1'—C7'—N2'—C11'	−161.88 (18)
C6—C7—N1—C8	1.5 (3)	C6'—C7'—N2'—C12'	175.38 (17)
N1—C7—N2—C11	−169.55 (17)	C10'—C11'—N2'—C7'	−150.07 (18)
C6—C7—N2—C12	165.38 (18)	C10'—C11'—N2'—C12'	53.3 (2)
C10—C11—N2—C7	−152.67 (18)	C13'—C12'—N2'—C7'	149.04 (18)
C10—C11—N2—C12	52.0 (2)	C13'—C12'—N2'—C11'	−53.6 (2)
C13—C12—N2—C7	151.52 (18)	N1'—C8'—O1'—C2'	179.24 (16)
C13—C12—N2—C11	−52.6 (2)	C9'—C8'—O1'—C2'	−0.6 (3)
N1—C8—O1—C2	179.71 (16)	O2'—C2'—O1'—C8'	179.05 (17)
C9—C8—O1—C2	−0.2 (3)	C3'—C2'—O1'—C8'	−0.4 (3)
O2—C2—O1—C8	179.79 (16)	C12'—C13'—O3'—C10'	−59.9 (2)
C3—C2—O1—C8	0.5 (3)	C11'—C10'—O3'—C13'	59.7 (2)

(ld489)

Crystal data

C15H15F3N2O2	F(000) = 648
Mr = 312.29	Dx = 1.457 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 11391 reflections
a = 8.9941 (5) Å	θ = 1.0–27.5°
b = 11.2954 (6) Å	µ = 0.12 mm^−1
c = 14.3536 (9) Å	T = 180 K
β = 102.537 (3)°	Unknown, orange
V = 1423.44 (14) Å^3	0.42 × 0.22 × 0.14 mm
Z = 4

Data collection

KappaCCD diffractometer	3199 independent reflections
Radiation source: fine-focus sealed tube	2235 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
Detector resolution: 9 pixels mm^-1	θmax = 27.4°, θmin = 3.8°
CCD scans	h = −11→11
Absorption correction: multi-scan (Blessing, 1997)	k = −12→14
Tmin = 0.958, Tmax = 0.998	l = −18→18
7357 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.127	All H-atom parameters refined
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0596P)^2 + 0.3202P] where P = (Fo^2 + 2Fc^2)/3
3199 reflections	(Δ/σ)max = 0.002
259 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.2477 (2)	0.78948 (17)	0.14985 (14)	0.0391 (4)
C2	0.80818 (19)	0.46523 (15)	0.07362 (12)	0.0325 (4)
C3	0.7898 (2)	0.55964 (16)	0.00517 (13)	0.0330 (4)
C4	0.67916 (19)	0.64196 (14)	0.00119 (12)	0.0290 (4)
C5	0.45757 (19)	0.71682 (15)	0.07080 (12)	0.0300 (4)
C6	0.36822 (19)	0.70197 (14)	0.13569 (12)	0.0305 (4)
C7	0.39573 (19)	0.59913 (14)	0.19546 (12)	0.0294 (4)
C8	0.59412 (18)	0.54420 (14)	0.13010 (11)	0.0277 (4)
C9	0.57626 (18)	0.63679 (14)	0.06469 (11)	0.0269 (4)
C10	0.1224 (2)	0.72198 (18)	0.18203 (15)	0.0398 (5)
C11	0.1795 (2)	0.64828 (17)	0.27112 (14)	0.0390 (4)
C12	0.3571 (3)	0.4805 (2)	0.32947 (19)	0.0539 (6)
C13	0.6682 (2)	0.74157 (16)	−0.06926 (13)	0.0378 (4)
C14	0.1864 (3)	0.8655 (2)	0.06277 (17)	0.0493 (6)
C15	0.0514 (3)	0.5755 (2)	0.29548 (18)	0.0517 (6)
F1	0.76268 (15)	0.72983 (11)	−0.12794 (9)	0.0596 (4)
F2	0.70122 (17)	0.84548 (10)	−0.02397 (10)	0.0636 (4)
F3	0.52873 (13)	0.75268 (10)	−0.12364 (8)	0.0505 (3)
H1	0.298 (3)	0.844 (2)	0.2072 (17)	0.057 (6)*
H3	0.863 (2)	0.5633 (16)	−0.0342 (13)	0.035 (5)*
H5	0.440 (2)	0.7812 (17)	0.0288 (14)	0.034 (5)*
H11	0.219 (2)	0.705 (2)	0.3271 (16)	0.053 (6)*
H10A	0.043 (2)	0.7740 (18)	0.1927 (14)	0.045 (5)*
H12A	0.346 (3)	0.509 (3)	0.395 (2)	0.088 (9)*
H14A	0.102 (3)	0.917 (2)	0.0727 (18)	0.067 (7)*
H15A	−0.036 (3)	0.628 (2)	0.2940 (18)	0.070 (8)*
H10B	0.071 (2)	0.6632 (19)	0.1288 (16)	0.051 (6)*
H12B	0.459 (4)	0.456 (3)	0.328 (3)	0.117 (12)*
H14B	0.264 (3)	0.918 (2)	0.0478 (16)	0.060 (7)*
H15B	0.080 (3)	0.537 (2)	0.3598 (19)	0.066 (7)*
H12C	0.292 (4)	0.419 (3)	0.315 (2)	0.092 (10)*
H14C	0.139 (3)	0.808 (3)	0.009 (2)	0.090 (9)*
H15C	0.021 (3)	0.507 (2)	0.2430 (18)	0.072 (7)*
N1	0.50978 (16)	0.52345 (12)	0.19248 (10)	0.0304 (3)
N2	0.30719 (17)	0.57286 (13)	0.25804 (11)	0.0357 (4)
O1	0.70763 (13)	0.46132 (10)	0.13396 (8)	0.0330 (3)
O2	0.90560 (14)	0.38881 (12)	0.08503 (10)	0.0439 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0448 (11)	0.0323 (9)	0.0432 (11)	0.0059 (8)	0.0163 (9)	−0.0015 (9)
C2	0.0264 (8)	0.0352 (9)	0.0364 (9)	0.0007 (7)	0.0077 (7)	−0.0013 (8)
C3	0.0280 (9)	0.0392 (10)	0.0339 (9)	−0.0017 (7)	0.0112 (7)	−0.0001 (8)
C4	0.0292 (8)	0.0298 (9)	0.0283 (8)	−0.0046 (7)	0.0067 (7)	−0.0016 (7)
C5	0.0346 (9)	0.0242 (8)	0.0320 (9)	−0.0011 (7)	0.0088 (7)	0.0018 (7)
C6	0.0327 (9)	0.0260 (8)	0.0345 (9)	−0.0007 (7)	0.0108 (7)	−0.0031 (7)
C7	0.0320 (9)	0.0299 (9)	0.0273 (8)	−0.0041 (7)	0.0091 (7)	−0.0036 (7)
C8	0.0261 (8)	0.0283 (8)	0.0281 (8)	−0.0017 (7)	0.0048 (7)	−0.0032 (7)
C9	0.0284 (8)	0.0261 (8)	0.0262 (8)	−0.0018 (7)	0.0056 (7)	−0.0004 (7)
C10	0.0333 (10)	0.0441 (11)	0.0449 (11)	0.0057 (9)	0.0148 (8)	−0.0020 (10)
C11	0.0384 (10)	0.0423 (11)	0.0401 (10)	−0.0010 (8)	0.0167 (8)	−0.0058 (9)
C12	0.0648 (16)	0.0514 (14)	0.0539 (14)	0.0100 (12)	0.0314 (12)	0.0199 (12)
C13	0.0406 (10)	0.0370 (10)	0.0400 (10)	0.0007 (8)	0.0177 (8)	0.0036 (8)
C14	0.0549 (14)	0.0436 (12)	0.0551 (13)	0.0190 (11)	0.0245 (11)	0.0107 (11)
C15	0.0439 (12)	0.0638 (14)	0.0524 (13)	−0.0065 (11)	0.0215 (10)	0.0027 (12)
F1	0.0637 (8)	0.0658 (8)	0.0623 (8)	0.0152 (6)	0.0419 (7)	0.0257 (7)
F2	0.0959 (11)	0.0341 (6)	0.0653 (8)	−0.0164 (6)	0.0275 (8)	0.0021 (6)
F3	0.0508 (7)	0.0548 (7)	0.0463 (6)	0.0126 (5)	0.0112 (5)	0.0194 (6)
N1	0.0319 (8)	0.0296 (7)	0.0313 (7)	0.0006 (6)	0.0100 (6)	0.0020 (6)
N2	0.0395 (8)	0.0346 (8)	0.0375 (8)	0.0019 (6)	0.0180 (7)	0.0031 (7)
O1	0.0302 (6)	0.0335 (7)	0.0369 (6)	0.0061 (5)	0.0110 (5)	0.0066 (5)
O2	0.0361 (7)	0.0437 (8)	0.0543 (8)	0.0103 (6)	0.0149 (6)	0.0066 (7)

Geometric parameters (Å, º)

C6—C7	1.433 (2)	C10—C11	1.519 (3)
C7—N1	1.343 (2)	C10—H10A	0.96 (2)
C8—N1	1.314 (2)	C10—H10B	1.04 (2)
C8—C9	1.391 (2)	C11—N2	1.475 (2)
C5—C9	1.416 (2)	C11—C15	1.517 (3)
C5—C6	1.366 (2)	C11—H11	1.03 (2)
C8—O1	1.377 (2)	C12—N2	1.464 (3)
C2—O1	1.3820 (19)	C12—H12A	1.01 (3)
C2—C3	1.435 (2)	C12—H12B	0.96 (4)
C3—C4	1.354 (2)	C12—H12C	0.91 (3)
C4—C9	1.434 (2)	C13—F1	1.326 (2)
C2—O2	1.215 (2)	C13—F3	1.332 (2)
C7—N2	1.356 (2)	C13—F2	1.343 (2)
C1—C6	1.513 (2)	C14—H14A	0.99 (3)
C1—C10	1.514 (3)	C14—H14B	0.97 (2)
C1—C14	1.518 (3)	C14—H14C	1.03 (3)
C1—H1	1.05 (2)	C15—H15A	0.98 (3)
C3—H3	0.954 (19)	C15—H15B	1.00 (3)
C4—C13	1.502 (2)	C15—H15C	1.07 (3)
C5—H5	0.936 (19)
C6—C1—C10	108.34 (15)	N2—C11—C15	111.58 (17)
C6—C1—C14	113.68 (16)	N2—C11—C10	109.87 (15)
C10—C1—C14	112.00 (18)	C15—C11—C10	110.87 (18)
C6—C1—H1	107.0 (12)	N2—C11—H11	108.0 (12)
C10—C1—H1	106.2 (12)	C15—C11—H11	108.1 (12)
C14—C1—H1	109.2 (12)	C10—C11—H11	108.3 (12)
O2—C2—O1	116.33 (15)	N2—C12—H12A	110.1 (16)
O2—C2—C3	126.35 (16)	N2—C12—H12B	110 (2)
O1—C2—C3	117.31 (14)	H12A—C12—H12B	113 (3)
C4—C3—C2	120.92 (16)	N2—C12—H12C	108 (2)
C4—C3—H3	122.5 (11)	H12A—C12—H12C	105 (2)
C2—C3—H3	116.4 (11)	H12B—C12—H12C	110 (3)
C3—C4—C9	120.98 (15)	F1—C13—F3	106.80 (15)
C3—C4—C13	118.88 (15)	F1—C13—F2	106.87 (15)
C9—C4—C13	120.11 (15)	F3—C13—F2	106.39 (15)
C6—C5—C9	121.79 (16)	F1—C13—C4	113.30 (15)
C6—C5—H5	119.6 (11)	F3—C13—C4	112.38 (15)
C9—C5—H5	118.6 (11)	F2—C13—C4	110.70 (15)
C5—C6—C7	117.18 (15)	C1—C14—H14A	111.6 (14)
C5—C6—C1	123.78 (16)	C1—C14—H14B	112.3 (14)
C7—C6—C1	118.99 (15)	H14A—C14—H14B	105.8 (19)
N1—C7—N2	116.36 (15)	C1—C14—H14C	106.5 (17)
N1—C7—C6	122.05 (15)	H14A—C14—H14C	106 (2)
N2—C7—C6	121.59 (15)	H14B—C14—H14C	114 (2)
N1—C8—O1	112.57 (14)	C11—C15—H15A	108.2 (15)
N1—C8—C9	126.49 (15)	C11—C15—H15B	112.9 (14)
O1—C8—C9	120.94 (14)	H15A—C15—H15B	109 (2)
C8—C9—C5	114.60 (15)	C11—C15—H15C	108.6 (13)
C8—C9—C4	117.62 (15)	H15A—C15—H15C	110 (2)
C5—C9—C4	127.77 (15)	H15B—C15—H15C	108.1 (19)
C1—C10—C11	113.25 (17)	C8—N1—C7	117.77 (14)
C1—C10—H10A	111.8 (12)	C7—N2—C12	119.01 (16)
C11—C10—H10A	109.1 (12)	C7—N2—C11	122.92 (15)
C1—C10—H10B	109.7 (11)	C12—N2—C11	116.87 (16)
C11—C10—H10B	106.4 (11)	C8—O1—C2	122.22 (13)
H10A—C10—H10B	106.3 (17)
C6—C7—N2—C11	−1.4 (3)	C13—C4—C9—C5	0.3 (3)
N1—C7—N2—C12	11.7 (3)	C6—C1—C10—C11	55.8 (2)
O2—C2—C3—C4	−177.94 (17)	C14—C1—C10—C11	−178.04 (17)
O1—C2—C3—C4	0.8 (2)	C1—C10—C11—N2	−51.8 (2)
C2—C3—C4—C9	−0.5 (3)	C1—C10—C11—C15	−175.60 (18)
C2—C3—C4—C13	177.75 (16)	C3—C4—C13—F1	6.6 (2)
C9—C5—C6—C7	−2.2 (2)	C9—C4—C13—F1	−175.14 (15)
C9—C5—C6—C1	175.43 (17)	C3—C4—C13—F3	127.75 (17)
C10—C1—C6—C5	149.84 (17)	C9—C4—C13—F3	−54.0 (2)
C14—C1—C6—C5	24.6 (3)	C3—C4—C13—F2	−113.45 (18)
C10—C1—C6—C7	−32.5 (2)	C9—C4—C13—F2	64.8 (2)
C14—C1—C6—C7	−157.71 (18)	O1—C8—N1—C7	179.68 (14)
C5—C6—C7—N1	3.8 (2)	C9—C8—N1—C7	−1.0 (2)
C1—C6—C7—N1	−174.01 (16)	N2—C7—N1—C8	177.59 (14)
C5—C6—C7—N2	−175.99 (15)	C6—C7—N1—C8	−2.2 (2)
C1—C6—C7—N2	6.2 (3)	C6—C7—N2—C12	−168.50 (19)
N1—C8—C9—C5	2.4 (2)	N1—C7—N2—C11	178.78 (16)
O1—C8—C9—C5	−178.35 (14)	C15—C11—N2—C7	147.17 (18)
N1—C8—C9—C4	−178.67 (15)	C10—C11—N2—C7	23.8 (2)
O1—C8—C9—C4	0.6 (2)	C15—C11—N2—C12	−45.5 (3)
C6—C5—C9—C8	−0.6 (2)	C10—C11—N2—C12	−168.90 (19)
C6—C5—C9—C4	−179.36 (16)	N1—C8—O1—C2	179.03 (14)
C3—C4—C9—C8	−0.1 (2)	C9—C8—O1—C2	−0.3 (2)
C13—C4—C9—C8	−178.40 (15)	O2—C2—O1—C8	178.48 (15)
C3—C4—C9—C5	178.59 (16)	C3—C2—O1—C8	−0.4 (2)

(ld473)

Crystal data

C17H19F3N2O	F(000) = 680
Mr = 324.34	Dx = 1.362 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9368 reflections
a = 12.1853 (5) Å	θ = 1.0–27.5°
b = 12.2242 (4) Å	µ = 0.11 mm^−1
c = 10.6361 (3) Å	T = 180 K
β = 93.4529 (11)°	Unknown, yellow
V = 1581.43 (9) Å^3	0.32 × 0.16 × 0.12 mm
Z = 4

Data collection

KappaCCD diffractometer	3601 independent reflections
Radiation source: fine-focus sealed tube	2179 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.062
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 3.7°
CCD scans	h = −15→15
Absorption correction: multi-scan (Blessing, 1997)	k = −15→15
Tmin = 0.943, Tmax = 0.989	l = −13→13
14885 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.123	All H-atom parameters refined
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0651P)^2] where P = (Fo^2 + 2Fc^2)/3
3601 reflections	(Δ/σ)max < 0.001
284 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.37858 (15)	0.10863 (13)	0.19150 (16)	0.0341 (4)
C2	0.05239 (15)	−0.19513 (14)	−0.18187 (16)	0.0341 (4)
C3	0.11890 (15)	−0.26681 (14)	−0.10184 (16)	0.0345 (4)
C4	0.19407 (14)	−0.22888 (12)	−0.01473 (15)	0.0290 (4)
C5	0.28973 (14)	−0.06881 (13)	0.09354 (16)	0.0296 (4)
C6	0.29987 (14)	0.04135 (13)	0.10744 (15)	0.0293 (4)
C7	0.23139 (14)	0.11227 (12)	0.03302 (15)	0.0292 (4)
C8	0.15392 (15)	0.07277 (13)	−0.05515 (16)	0.0303 (4)
C9	0.14378 (14)	−0.04151 (12)	−0.07069 (14)	0.0272 (4)
C10	0.21080 (14)	−0.11406 (12)	0.00472 (15)	0.0274 (4)
C11	0.31771 (17)	0.22020 (14)	0.18754 (18)	0.0385 (5)
C12	0.17909 (18)	0.30711 (15)	0.0320 (2)	0.0398 (5)
C13	−0.00241 (18)	−0.00971 (16)	−0.2378 (2)	0.0392 (5)
C14	0.26336 (16)	−0.31053 (13)	0.05997 (17)	0.0360 (4)
C15	0.3930 (2)	0.06468 (18)	0.32525 (19)	0.0451 (5)
C16	0.48967 (18)	0.11344 (19)	0.1319 (2)	0.0467 (5)
C17	0.3878 (2)	0.32150 (17)	0.2094 (3)	0.0542 (6)
F1	0.26308 (9)	−0.29590 (8)	0.18444 (9)	0.0456 (3)
F2	0.36909 (9)	−0.30578 (9)	0.03196 (11)	0.0535 (3)
F3	0.23105 (10)	−0.41370 (7)	0.03869 (11)	0.0567 (4)
H3	0.1077 (15)	−0.3436 (14)	−0.1152 (15)	0.037 (5)*
H5	0.3379 (15)	−0.1191 (13)	0.1455 (15)	0.032 (4)*
H8	0.1097 (15)	0.1192 (13)	−0.1019 (16)	0.032 (5)*
H11	0.2583 (17)	0.2200 (14)	0.2547 (18)	0.047 (5)*
H12A	0.1440 (18)	0.3053 (17)	−0.054 (2)	0.059 (6)*
H13A	−0.0493 (18)	−0.0488 (17)	−0.2926 (19)	0.056 (6)*
H15A	0.4327 (18)	0.1160 (16)	0.381 (2)	0.055 (6)*
H16A	0.4774 (17)	0.1451 (15)	0.045 (2)	0.052 (6)*
H17A	0.431 (2)	0.3160 (17)	0.292 (2)	0.067 (7)*
H12B	0.123 (2)	0.3111 (18)	0.096 (2)	0.079 (8)*
H13B	−0.0482 (19)	0.0350 (17)	−0.186 (2)	0.063 (7)*
H15B	0.321 (2)	0.0536 (17)	0.3611 (19)	0.064 (7)*
H16B	0.5442 (18)	0.1583 (16)	0.1821 (18)	0.056 (6)*
H17B	0.341 (2)	0.3878 (18)	0.215 (2)	0.070 (7)*
H12C	0.2183 (18)	0.3748 (18)	0.0362 (19)	0.057 (6)*
H13C	0.043 (2)	0.0356 (19)	−0.285 (2)	0.073 (7)*
H15C	0.4393 (19)	−0.0050 (19)	0.3299 (19)	0.065 (6)*
H16C	0.5235 (18)	0.0373 (18)	0.1283 (19)	0.058 (6)*
H17C	0.438 (2)	0.3315 (17)	0.139 (2)	0.065 (7)*
N1	0.06657 (11)	−0.08403 (10)	−0.15980 (12)	0.0298 (3)
N2	0.25658 (12)	0.21959 (10)	0.06281 (13)	0.0343 (4)
O2	−0.01422 (11)	−0.22857 (10)	−0.26542 (12)	0.0471 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0344 (11)	0.0314 (9)	0.0358 (10)	−0.0055 (8)	−0.0025 (8)	−0.0057 (7)
C2	0.0367 (11)	0.0281 (9)	0.0367 (9)	−0.0076 (7)	−0.0035 (8)	−0.0020 (7)
C3	0.0419 (12)	0.0223 (9)	0.0390 (10)	−0.0050 (8)	−0.0021 (8)	−0.0018 (7)
C4	0.0312 (10)	0.0240 (8)	0.0319 (9)	−0.0006 (7)	0.0018 (8)	0.0017 (7)
C5	0.0279 (10)	0.0267 (9)	0.0337 (9)	0.0021 (7)	−0.0028 (8)	0.0002 (7)
C6	0.0272 (10)	0.0272 (9)	0.0333 (9)	−0.0023 (7)	−0.0006 (7)	−0.0038 (7)
C7	0.0320 (10)	0.0234 (8)	0.0323 (9)	−0.0033 (7)	0.0025 (8)	−0.0026 (7)
C8	0.0323 (10)	0.0248 (8)	0.0332 (9)	0.0008 (7)	−0.0022 (8)	0.0013 (7)
C9	0.0278 (10)	0.0244 (9)	0.0292 (8)	−0.0021 (7)	−0.0002 (7)	−0.0015 (7)
C10	0.0282 (9)	0.0221 (8)	0.0321 (9)	0.0005 (7)	0.0024 (7)	−0.0023 (7)
C11	0.0455 (12)	0.0305 (10)	0.0386 (10)	−0.0055 (8)	−0.0043 (9)	−0.0069 (8)
C12	0.0467 (13)	0.0227 (10)	0.0500 (13)	−0.0006 (8)	0.0016 (11)	0.0010 (8)
C13	0.0414 (12)	0.0320 (10)	0.0425 (11)	−0.0003 (9)	−0.0130 (10)	0.0033 (9)
C14	0.0400 (12)	0.0266 (10)	0.0412 (10)	−0.0011 (8)	0.0009 (8)	−0.0003 (8)
C15	0.0515 (14)	0.0441 (12)	0.0385 (11)	−0.0039 (11)	−0.0075 (10)	−0.0044 (9)
C16	0.0371 (12)	0.0510 (13)	0.0512 (13)	−0.0104 (10)	−0.0025 (10)	−0.0085 (11)
C17	0.0670 (17)	0.0357 (12)	0.0579 (15)	−0.0130 (11)	−0.0123 (13)	−0.0090 (10)
F1	0.0558 (8)	0.0426 (6)	0.0375 (6)	0.0063 (5)	−0.0037 (5)	0.0076 (5)
F2	0.0396 (7)	0.0523 (7)	0.0693 (8)	0.0155 (5)	0.0086 (6)	0.0117 (6)
F3	0.0759 (9)	0.0204 (5)	0.0711 (8)	0.0004 (5)	−0.0183 (6)	0.0024 (5)
N1	0.0311 (8)	0.0248 (7)	0.0327 (8)	−0.0016 (6)	−0.0052 (6)	0.0018 (6)
N2	0.0427 (10)	0.0217 (7)	0.0380 (8)	−0.0029 (6)	−0.0024 (7)	−0.0024 (6)
O2	0.0557 (9)	0.0343 (7)	0.0485 (8)	−0.0106 (6)	−0.0194 (7)	−0.0018 (6)

Geometric parameters (Å, º)

C6—C7	1.412 (2)	C11—C17	1.514 (3)
C7—C8	1.377 (2)	C11—H11	1.05 (2)
C8—C9	1.411 (2)	C12—N2	1.451 (2)
C9—C10	1.420 (2)	C12—H12A	0.98 (2)
C5—C10	1.419 (2)	C12—H12B	0.99 (3)
C5—C6	1.359 (2)	C12—H12C	0.95 (2)
C9—N1	1.395 (2)	C13—N1	1.462 (2)
C2—N1	1.387 (2)	C13—H13A	0.92 (2)
C2—C3	1.437 (2)	C13—H13B	0.97 (2)
C3—C4	1.345 (2)	C13—H13C	0.95 (2)
C4—C10	1.432 (2)	C14—F1	1.336 (2)
C2—O2	1.236 (2)	C14—F3	1.3365 (19)
C7—N2	1.380 (2)	C14—F2	1.341 (2)
C1—C6	1.514 (2)	C15—H15A	0.97 (2)
C1—C15	1.521 (3)	C15—H15B	0.98 (2)
C1—C16	1.530 (3)	C15—H15C	1.02 (2)
C1—C11	1.552 (2)	C16—H16A	1.00 (2)
C3—H3	0.957 (17)	C16—H16B	0.99 (2)
C4—C14	1.503 (2)	C16—H16C	1.02 (2)
C5—H5	0.994 (17)	C17—H17A	1.01 (2)
C8—H8	0.910 (18)	C17—H17B	0.99 (2)
C11—N2	1.482 (2)	C17—H17C	1.00 (2)
C6—C1—C15	113.20 (15)	H12A—C12—H12B	111 (2)
C6—C1—C16	108.74 (14)	N2—C12—H12C	108.2 (13)
C15—C1—C16	110.19 (17)	H12A—C12—H12C	104.5 (17)
C6—C1—C11	100.18 (14)	H12B—C12—H12C	106.8 (18)
C15—C1—C11	111.36 (16)	N1—C13—H13A	110.5 (13)
C16—C1—C11	112.86 (16)	N1—C13—H13B	110.9 (12)
O2—C2—N1	120.99 (16)	H13A—C13—H13B	107.0 (18)
O2—C2—C3	123.12 (15)	N1—C13—H13C	109.3 (14)
N1—C2—C3	115.89 (15)	H13A—C13—H13C	109.0 (18)
C4—C3—C2	122.27 (15)	H13B—C13—H13C	110.1 (19)
C4—C3—H3	121.7 (11)	F1—C14—F3	106.01 (13)
C2—C3—H3	116.0 (11)	F1—C14—F2	105.91 (15)
C3—C4—C10	121.50 (15)	F3—C14—F2	106.29 (14)
C3—C4—C14	118.20 (14)	F1—C14—C4	113.58 (14)
C10—C4—C14	120.27 (14)	F3—C14—C4	112.75 (15)
C6—C5—C10	120.80 (16)	F2—C14—C4	111.74 (14)
C6—C5—H5	120.3 (9)	C1—C15—H15A	111.7 (12)
C10—C5—H5	118.9 (9)	C1—C15—H15B	110.9 (12)
C5—C6—C7	120.01 (15)	H15A—C15—H15B	105.8 (17)
C5—C6—C1	130.74 (15)	C1—C15—H15C	111.9 (12)
C7—C6—C1	109.22 (13)	H15A—C15—H15C	104.8 (17)
C8—C7—N2	128.57 (15)	H15B—C15—H15C	111.5 (17)
C8—C7—C6	121.60 (14)	C1—C16—H16A	108.0 (12)
N2—C7—C6	109.83 (14)	C1—C16—H16B	112.3 (12)
C7—C8—C9	118.58 (16)	H16A—C16—H16B	109.8 (16)
C7—C8—H8	120.8 (11)	C1—C16—H16C	110.5 (12)
C9—C8—H8	120.6 (11)	H16A—C16—H16C	110.8 (16)
N1—C9—C8	119.94 (14)	H16B—C16—H16C	105.4 (17)
N1—C9—C10	119.49 (13)	C11—C17—H17A	110.1 (12)
C8—C9—C10	120.57 (15)	C11—C17—H17B	111.1 (14)
C5—C10—C9	118.43 (14)	H17A—C17—H17B	105.8 (18)
C5—C10—C4	124.28 (15)	C11—C17—H17C	110.2 (13)
C9—C10—C4	117.29 (14)	H17A—C17—H17C	110.8 (19)
N2—C11—C17	112.94 (16)	H17B—C17—H17C	108.7 (17)
N2—C11—C1	103.51 (13)	C2—N1—C9	123.48 (14)
C17—C11—C1	116.77 (18)	C2—N1—C13	116.81 (14)
N2—C11—H11	106.2 (10)	C9—N1—C13	119.69 (13)
C17—C11—H11	107.7 (10)	C7—N2—C12	121.09 (15)
C1—C11—H11	109.2 (10)	C7—N2—C11	107.65 (13)
N2—C12—H12A	115.7 (13)	C12—N2—C11	118.90 (14)
N2—C12—H12B	110.4 (14)
C6—C7—N2—C11	−18.60 (19)	C14—C4—C10—C5	−0.9 (2)
C8—C7—N2—C12	20.5 (3)	C3—C4—C10—C9	0.8 (2)
O2—C2—C3—C4	177.31 (18)	C14—C4—C10—C9	178.89 (15)
N1—C2—C3—C4	−3.0 (3)	C6—C1—C11—N2	−28.76 (17)
C2—C3—C4—C10	1.1 (3)	C15—C1—C11—N2	−148.76 (16)
C2—C3—C4—C14	−177.06 (16)	C16—C1—C11—N2	86.70 (18)
C10—C5—C6—C7	0.0 (2)	C6—C1—C11—C17	−153.51 (17)
C10—C5—C6—C1	−178.02 (16)	C15—C1—C11—C17	86.5 (2)
C15—C1—C6—C5	−44.0 (3)	C16—C1—C11—C17	−38.1 (2)
C16—C1—C6—C5	78.8 (2)	C3—C4—C14—F1	−127.99 (17)
C11—C1—C6—C5	−162.70 (18)	C10—C4—C14—F1	53.8 (2)
C15—C1—C6—C7	137.77 (17)	C3—C4—C14—F3	−7.4 (2)
C16—C1—C6—C7	−99.41 (17)	C10—C4—C14—F3	174.45 (15)
C11—C1—C6—C7	19.12 (17)	C3—C4—C14—F2	112.27 (18)
C5—C6—C7—C8	−0.4 (2)	C10—C4—C14—F2	−65.9 (2)
C1—C6—C7—C8	177.98 (15)	O2—C2—N1—C9	−177.10 (16)
C5—C6—C7—N2	−179.73 (14)	C3—C2—N1—C9	3.2 (2)
C1—C6—C7—N2	−1.32 (18)	O2—C2—N1—C13	1.3 (2)
N2—C7—C8—C9	179.02 (16)	C3—C2—N1—C13	−178.38 (16)
C6—C7—C8—C9	−0.1 (2)	C8—C9—N1—C2	179.20 (15)
C7—C8—C9—N1	−179.58 (15)	C10—C9—N1—C2	−1.5 (2)
C7—C8—C9—C10	1.1 (2)	C8—C9—N1—C13	0.8 (2)
C6—C5—C10—C9	0.9 (2)	C10—C9—N1—C13	−179.86 (16)
C6—C5—C10—C4	−179.28 (16)	C6—C7—N2—C12	−160.24 (16)
N1—C9—C10—C5	179.18 (14)	C8—C7—N2—C11	162.17 (17)
C8—C9—C10—C5	−1.5 (2)	C17—C11—N2—C7	157.40 (18)
N1—C9—C10—C4	−0.6 (2)	C1—C11—N2—C7	30.20 (18)
C8—C9—C10—C4	178.70 (15)	C17—C11—N2—C12	−60.0 (3)
C3—C4—C10—C5	−179.00 (16)	C1—C11—N2—C12	172.83 (16)